CN102108047B - Method for preparing 2,3,5-trimethylhydroquinone - Google Patents
Method for preparing 2,3,5-trimethylhydroquinone Download PDFInfo
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- CN102108047B CN102108047B CN 201010574016 CN201010574016A CN102108047B CN 102108047 B CN102108047 B CN 102108047B CN 201010574016 CN201010574016 CN 201010574016 CN 201010574016 A CN201010574016 A CN 201010574016A CN 102108047 B CN102108047 B CN 102108047B
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Abstract
The invention discloses a method for preparing 2,3,5-trimethylhydroquinone, which comprises oxidizing 2,3,6-trimethylphenol with pure oxygen or oxygen-enriched gas in water serving as a reaction medium in the presence of a catalyst consisting of copper halide and lithium halide and a phase transfer catalyst to obtain 2,3,5-trimethylhydroquinone. In the method disclosed by the invention, organic solvent is not added, the production safety is ensured, the operation is simplified, the energy cost is greatly reduced, the yield of the obtained product is over 90 percent, and the purity of the obtained product is over 99.5 percent. Thus, the method is suitable for industrial mass production.
Description
Technical field
The present invention relates to a kind of preparation 2,3, the method for 5-trimethylammonium para benzoquinone.
Background technology
2,3,5-trimethylammonium para benzoquinone is the important intermediate of synthetic alpha-tocopherol (vitamin-E), and 2,3,6-pseudocuminol is oxidized to 2,3,5-trimethylammonium para benzoquinone many disclosed methods.Used inorganic oxidizer such as potassium permanganate, Manganse Dioxide, plumbous oxide in the disclosed method, must consume the catalyzer of stoichiometry, and produce the pollution waste liquid of more reducing metal, this waste liquid needs higher cost to dispose or regenerate.
US3796732 has described the use cupric chloride as catalyzer, is that reaction solvent carries out homogeneous reaction with DMF, and the recovery suitability for industrialized production of catalyzer and DMF is pretty troublesome, and cost recovery is higher.
CN1024188 has described and has used cupric chloride and lithium chloride to be catalyzer, and the mixed solvent of forming with the Fatty Alcohol(C12-C14 and C12-C18) of aromatic hydrocarbons and 1-4 carbon atom is convenient to after reaction finishes separate and purify as reaction solvent, and the water that contains catalyzer can be applied mechanically repeatedly.Because the reaction solvent flash-point is lower, reaction system is again to react under pure oxygen or excess oxygen, therefore has bigger production safety hidden danger.
It is catalyzer that CN1293182 has described with cupric chloride and transition metal halide or rare earth element halogenide, is reaction solvent with the Fatty Alcohol(C12-C14 and C12-C18) of water and 6-8 carbon atom, because the existence of low-flash solvent has bigger production safety hidden danger equally.
EP0369823 is with copper halide and nitrogenous compound such as azanol, amine or amine salt is as combination catalyst accordingly, and nitrogenous catalyzer can decompose under oxidizing condition, can not reclaim, and therefore can increase cost, equally also needs the alcohol of 1-10 carbon atom as solvent.
EP0387820 is solvent with the Fatty Alcohol(C12-C14 and C12-C18) of 12-18 carbon atom, because the boiling point of solvent is higher, product is difficult for and separated from solvent, and energy consumption is higher, is not suitable for industrial applications.
EP127888 is catalyzer with the aqueous solution of cupric chloride lithium, and it is excessive greatly that the amount of catalyzer needs, and Preparation of catalysts is comparatively complicated, needs the title complex of preparation means of trivalent copper, and the Preparation of Catalyst cost is higher.
The new carboxylic acid that CN1319582 discloses with 8-11 carbon atom is solvent, be solvent with the neodecanoic acid particularly, and the neodecanoic acid boiling point is higher, has product and separated from solvent trouble equally, the problem that separation costs is high.
It is reaction solvent that CN101113131A has described the ionic liquid that constitutes with imidazoles, quaternary ammonium and pyridylium and acid ion, reaction back straight run distillation, but a large amount of distillation residue and ionic liquids mix, and ionic liquid is difficult to directly apply mechanically, and is not suitable for suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of preparation 2,3, the novel method of 5-trimethylammonium para benzoquinone is to overcome the weak point of above-mentioned technology.
Disclosed preparation 2,3 of the present invention, the method for 5-trimethylammonium para benzoquinone comprises the steps: 2,3,6-pseudocuminol adds phase-transfer catalyst under copper halide and lithium halide catalysis, be solvent with water, oxidation prepares 2,3,5-trimethylammonium para benzoquinone under pure oxygen or oxygen rich gas condition.
Embodiment
In this manual, unless have other the explanation, each optimal technical scheme and more preferably the technical characterictic of technical scheme can be combined to form new technical scheme mutually.For concise and to the point purpose, the applicant has omitted the specific descriptions of these combinations in specification sheets, yet the technical scheme after all these technical characterictic combinations all should be considered to be recorded in this specification sheets so that clear and definite mode is written.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable among the present invention.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
In some preferred embodiments, described phase-transfer catalyst is quaternary ammonium salt or polyethers phase-transfer catalyst.
In some preferred embodiments, the mol ratio of 2,3,6-pseudocuminol and quaternary ammonium salt or polyethers phase-transfer catalyst is 1: 0.001-0.1 is preferably 1: 0.01-0.1, more preferably 1: 0.02-0.05.
In some preferred embodiments, quaternary ammonium salt phase transfer catalyst is selected from one or more of benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride or Dodecyl trimethyl ammonium chloride.
In some preferred embodiments, the polyethers phase-transfer catalyst is selected from polyoxyethylene glycol, for example a kind of among PEG200, PEG300, PEG400, the PEG600.
In some preferred embodiments, described copper halide is cupric chloride, and lithium halide is lithium chloride.
In some preferred embodiments, the mol ratio of 2,3,6-pseudocuminol and copper halide is 1: 1-2, the mol ratio of 2,3,6-pseudocuminol and lithium halide is 1: 1-3.
Temperature of reaction can change in wide scope, is preferably 20-120 ℃, more preferably 30-60 ℃.
In some preferred embodiments, pure oxygen is used in reaction, also can be oxygen rich gas, or air, and it is gas more than 40% that described oxygen rich gas refers to oxygen level.
In some preferred embodiments, raw material is added drop-wise in the system with molten state, the dropping time is 13.6 grams 2,3,6-pseudocuminol/1-5 hour, be preferably 1-3 hour, the hexamethyl biphenol that drips too fast generation can be more, general 1-3 hour is more suitable, drips slowly to instead producing active influence.
Reaction times is depended on the pressure of oxygen of reaction and the effect of temperature of reaction and stirring, generally speaking, after dripping 2,3,6-pseudocuminol, reacts and finishes in 3-5 hour.
Method of the present invention can be reacted under normal pressure, also can carry out under certain pressure, and pressure can be 0.01-12MPa, preferred 0.1-10MPa, more preferably 0.1-1MPa, more preferably 0.3-1MPa.
Method of the present invention can also use ultrasonic wave to promote reaction.Used ultrasonic generator is can buy on the market, and ultrasonic probe can directly contact with reaction solution, also can indirect contact.
Ultrasonic frequency can be that low frequency also can be high frequency, can be 20KHz-100MHz, preferred 20KHz-2MHz, more preferably 20KHz-1MHz.
Ultrasonic wave can be opened also in reaction process always and can intermittently open according to program.
This reaction need not add any organic solvent, not only guaranteed the security of producing, also simplified operation, direct layering after reaction is finished, oil reservoir obtains product by the direct underpressure distillation of ordinary method, has avoided reclaiming the trouble of solvent, greatly reduce energy consumption, the catalyzer water layer can be applied mechanically repeatedly, and the product that obtains has yield and 99.5% above purity more than 90%, suitable industrialized production.
Embodiment
The invention will be further described by the following examples.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
In 150 milliliters of four-hole bottles of prolong, stirring rake, addition funnel and ventpipe are housed, add 80 gram water, 17 gram copper chloride dihydrates and 7 gram Lithium chloride (anhydrous)s, add 0.68 gram benzyltriethylammoinium chloride again, vigorous stirring, be heated to 40 ℃, by the Glass tubing aerating oxygen, flow is 300 ml/min, begins to drip 2 of fusion, 3,6-pseudocuminol 13.6 grams added in 2 hours, reacted after dripping 4 hours again.After reaction finishes, directly get oil reservoir and do the GC analysis, 2,3,5-trimethylbenzoquinone purity is 93%.Get the oil phase underpressure distillation, obtain 2,3,5-trimethylbenzoquinone, 13.6 grams, yield is 90.0%, is GC again and analyzes, and purity is 99.5%.MS：m/z?150(M
+).。
Embodiment 2
150 milliliters of four-hole bottles that prolong, stirring rake, addition funnel and ventpipe are housed are placed in the ultrasound reactor, add 80 gram water, 17 gram copper chloride dihydrates and 7 gram Lithium chloride (anhydrous)s, add 0.68 gram benzyltriethylammoinium chloride again, vigorous stirring, be heated to 40 ℃, by the Glass tubing aerating oxygen, flow is 300 ml/min, open ultrasonic wave simultaneously, ultrasonic frequency is 20KHz, begins to drip 2 of fusion, 3,6-pseudocuminol 13.6 grams added in 2 hours, reacted after dripping 4 hours again.After reaction finishes, directly get oil reservoir and do the GC analysis, 2,3,5-trimethylbenzoquinone purity is 94%.Get the oil phase underpressure distillation, obtain 2,3,5-trimethylbenzoquinone, 13.7 grams, yield is 91.3%, is GC again and analyzes, and purity is 99.6%.
Embodiment 3
150 milliliters of four-hole bottles that prolong, stirring rake, addition funnel and ventpipe are housed are placed in the ultrasound reactor, add 80 gram water, 17 gram copper chloride dihydrates and 7 gram Lithium chloride (anhydrous)s, add 0.6 gram PEG300 again, vigorous stirring is heated to 40 ℃, by the Glass tubing aerating oxygen, flow is 300 ml/min, open ultrasonic wave simultaneously, ultrasonic frequency is 20KHz, begins to drip 2 of fusion, 3,6-pseudocuminol 13.6 grams added in 2 hours, reacted after dripping 4 hours again.After reaction finishes, directly get oil reservoir and do the GC analysis, 2,3,5-trimethylbenzoquinone purity is 94%.Get the oil phase underpressure distillation, obtain 2,3,5-trimethylbenzoquinone, 13.8 grams, yield is 92.0%, is GC again and analyzes, and purity is 99.7%.
Embodiment 4
In 150 milliliters of autoclaves, insert the ultrasonic stirring rod, frequency is 20KHZ, add 80 gram water, 17 gram copper chloride dihydrates and 7 gram Lithium chloride (anhydrous)s, add 0.68 gram benzyltriethylammoinium chloride again, vigorous stirring, be heated to 40 ℃, aerating oxygen is forced into 0.3MPa, reducing valve is set to 0.3MPa, opens ultrasonic wave simultaneously, and ultrasonic frequency is 20KHz, begin to drip 2,3 of fusion, 6-pseudocuminol 13.6 grams, add in 2 hours, reacted again after dripping 2 hours.After reaction finishes, get oil reservoir and do the GC analysis, 2,3,5-trimethylbenzoquinone purity is 96.50%.Get the oil phase underpressure distillation, obtain 2,3,5-trimethylbenzoquinone, 14.2 grams, yield is 94.6%, is GC again and analyzes, and purity is 99.9%.
Claims (18)
1. a method for preparing 2,3,5-trimethylammonium para benzoquinone is characterized in that, comprise the steps: 2,3,6-pseudocuminol under copper halide and lithium halide catalysis, add phase-transfer catalyst, be solvent with water, oxidation prepares 2,3,5-trimethylbenzoquinone under pure oxygen or oxygen rich gas condition.
2. the method for claim 1 is characterized in that, temperature of reaction is 20-120 ℃.
3. the method for claim 1 is characterized in that, reaction pressure is normal pressure.
4. the method for claim 1 is characterized in that, reaction pressure is 0.01-12MPa.
5. the method for claim 1 is characterized in that, reaction pressure 0.3-1MPa.
6. the method for claim 1 is characterized in that, described phase-transfer catalyst is quaternary ammonium salt or polyethers phase-transfer catalyst.
7. method as claimed in claim 6, it is characterized in that described quaternary ammonium salt phase transfer catalyst is selected from one or more of benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride or Dodecyl trimethyl ammonium chloride.
8. method as claimed in claim 6, the mol ratio that it is characterized in that 2,3,6-pseudocuminol and quaternary ammonium salt is 1:0.001-0.1.
9. method as claimed in claim 6, the mol ratio that it is characterized in that 2,3,6-pseudocuminol and quaternary ammonium salt is 1:0.01 – 0.1.
10. method as claimed in claim 6 is characterized in that, described polyethers phase-transfer catalyst is selected from polyoxyethylene glycol.
11. method as claimed in claim 10 is characterized in that, described polyoxyethylene glycol is selected from PEG200, PEG300, PEG400 or PEG600.
12. method as claimed in claim 10 is characterized in that, the mol ratio of 2,3,6-pseudocuminol and polyethers phase-transfer catalyst is 1:0.001-0.1.
13. method as claimed in claim 10 is characterized in that, the mol ratio of 2,3,6-pseudocuminol and polyethers phase-transfer catalyst is 1:0.01-0.1.
14. the method for claim 1 is characterized in that, also uses ultrasonic wave to promote reaction in reaction process.
15. method as claimed in claim 14 is characterized in that, frequency of ultrasonic is 20KHz-100MHz.
16. method as claimed in claim 14 is characterized in that, frequency of ultrasonic is 20KHz-2MHz.
17. the method for claim 1 is characterized in that, described copper halide is cupric chloride, and lithium halide is lithium chloride.
18. the method for claim 1 is characterized in that, the mol ratio of 2,3,6-pseudocuminol and copper halide is 1:1-2, and the mol ratio of 2,3,6-pseudocuminol and lithium halide is 1:1-3.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102584559B (en) * | 2012-01-10 | 2013-10-16 | 西北化工研究院 | Method for separating and purifying 2,3,5-trimethyl benzoquinone |
| CN103787850B (en) * | 2012-11-01 | 2015-10-21 | 中国科学院大连化学物理研究所 | The method of a kind of quinhydrones oxidation quinone processed |
| CN106699537B (en) * | 2013-07-02 | 2021-04-13 | 巴斯夫欧洲公司 | Method for producing 2,3, 5-trimethylbenzoquinone by oxidation of 2,3, 6-trimethylphenol |
| CN104292095A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for direct oxidation of phenol compound to prepare p-benzoquinone compound |
| CN104557502B (en) * | 2015-01-05 | 2020-06-16 | 吴嘉 | Method for continuously preparing 2, 3, 5-trimethylbenzoquinone |
| CN105693490B (en) * | 2016-03-11 | 2018-02-23 | 南京工业大学 | Method for preparing 2,3, 5-trimethylbenzoquinone by oxidation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319582A (en) * | 2000-03-09 | 2001-10-31 | 德古萨股份公司 | Process for preparing 2,3,5-trimethyl-p-benzoquinone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319582A (en) * | 2000-03-09 | 2001-10-31 | 德古萨股份公司 | Process for preparing 2,3,5-trimethyl-p-benzoquinone |
Non-Patent Citations (2)
| Title |
|---|
| Hari Sankar Das.Straightforward synthesis of substituted p-Quinones:isolation of a key intermediate and use as a bridging ligand in a diruthenium complex.《Chem.Eur.J.》.2010,第16卷(第10期), |
| Straightforward synthesis of substituted p-Quinones:isolation of a key intermediate and use as a bridging ligand in a diruthenium complex;Hari Sankar Das;《Chem.Eur.J.》;20100308;第16卷(第10期);第2977页Scheme 1；第2798页左栏第2段 * |
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Owner name: SHANGHAI HEGNO PHARMACEUTICAL DEVELOPMENT CO., LTD Free format text: FORMER OWNER: DISAINO MEDICINE DEVELOPMENT CO., LTD, SHANGHAI Effective date: 20110817 |
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Effective date of registration: 20110817 Address after: 201203 Zhang Heng Road, Shanghai, Pudong New Area, No. 1479 Applicant after: Shanghai Hegno Pharmaceuticals Holding Co., Ltd. Co-applicant after: Dafeng Haijianuo Pharmaceutical Co., Ltd. Address before: 201203 Zhang Heng road Shanghai, Pudong New Area Zhangjiang hi tech Park No. 1479 Applicant before: Disaino Medicine Development Co., Ltd, Shanghai Co-applicant before: Shanghai Hegno Pharmaceuticals Holding Co., Ltd. Co-applicant before: Dafeng Haijianuo Pharmaceutical Co., Ltd. |
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